KR20010022409A - Acrylic resin film and laminated film containing the same - Google Patents

Abstract

The present invention relates to an acrylic resin composition containing 95 to 50 parts by weight of an acrylic resin having a glass transition temperature of 60 to 110 ° C. and a weight average molecular weight of 70,000 to 600,000, and 5 to 50 parts by weight of a multilayer structured acrylic polymer including a rubber elastic layer. Acrylic resin film which consists of; And it relates to a laminated film consisting of the acrylic resin film and at least one other resin film. The acrylic resin film and the laminated film thereof exhibit excellent performance when used as an injection molding co-adhesive film or an agricultural film, a display film, a masking film, a paint substitute film, and the like.

Description

Acrylic resin film and laminated film thereof {ACRYLIC RESIN FILM AND LAMINATED FILM CONTAINING THE SAME}

Background Art Conventionally, molded articles molded by injection molding have been used for interiors of automobiles, exteriors of home appliances, and the like. In order to decorate such a molded body, for example, a decorated resin film is bonded to the molded body at the same time as the molded body is formed by the injection molding simultaneous bonding method.

The injection molding co-adhesion method is a method of arranging a film in advance between female and female molds during injection molding, injecting molten resin into a cavity of a positive mold, and molding the molten resin and adhering the film to the surface thereof (for example, Japanese Patent Publication No. 63-6339 (U.S. Patent No. 4,639,341), Japanese Patent Application Laid-Open No. Hei 4-9647, Japanese Patent Application Laid-open No. Hei 7-9484, Lamination method, transfer printing method, etc. It is also called. An acrylic resin film is known as a film used for such an injection molding co-adhesion method, and printing patterns are formed on one or both surfaces thereof, for example.

Moreover, since an acryl-type resin film is excellent in weatherability, it is used also as a film for coating on the surface of polycarbonate-type resin sheets, etc. (Japanese Unexamined-Japanese-Patent No. 47-19119, Unexamined-Japanese-Patent No. 55-59929).

However, conventional acrylic resin films are not sufficiently satisfactory in terms of thickness, surface smoothness, surface hardness, and the like.

Therefore, the present inventors have diligently studied to develop an acrylic resin film satisfying sufficient thickness, surface smoothness and surface hardness at the same time. As a result, an acrylic resin having a glass transition temperature of 60 to 110 ° C. and a weight average molecular weight of 7 to 600,000 is obtained. A film made of an acrylic resin composition containing a resin and an acrylic polymer having a multilayer structure including a rubber elastic layer has a sufficient thickness, smoothness of the surface, and surface hardness, and the acrylic resin film and its laminated film are injected. It is suitable for various uses such as molded co-adhesive film, agricultural film, display film, masking film, and paint substitute film, especially when the film colored or printed on the film is laminated compared with conventional acrylic film. The present invention has been found by discovering the excellent depth and printability of patterns. .

Disclosure of the Invention

The present invention relates to an acrylic resin composition containing 95 to 50 parts by weight of an acrylic resin having a glass transition temperature of 60 to 110 ° C. and a weight average molecular weight of 70,000 to 600,000, and 5 to 50 parts by weight of a multilayer structured acrylic polymer including a rubber elastic layer. Provided is an acrylic resin film.

It is made by coloring this film, and when laminated | stacked, the coloring film which expresses a sense of depth, metallic tone, etc. is provided.

The laminated | multilayer film formed by laminating | stacking films, such as a soft vinyl chloride film, on this acrylic resin film is provided.

Moreover, the laminated molded object formed by adhering these films to molded objects, such as a polycarbonate resin, is provided.

It further provides the use of these films as agricultural films, display films, masking films, paint substitute films.

Although the glass transition temperature of acrylic resin is generally the range of about 30 degreeC-110 degreeC, in the acrylic resin used by this invention, it is necessary to be 60 degreeC-110 degreeC, Preferably it is the range of 75-105 degreeC. The glass transition temperature is measured by using a differential scanning calorimetry under the condition of a heating rate of 10 ° C./min under N ₂ air flow, and the endothermic start temperature observed at that time is taken as the glass transition temperature. If the glass transition temperature is less than about 60 ° C., a film of sufficient surface hardness tends not to be obtained. Acrylic resins having a glass transition temperature of about 110 ° C. or more have a crosslinked structure and are difficult to mold.

In addition, the weight average molecular weight is about 70,000 to 60 if necessary, preferably in the range of about 120,000 to 300,000. Such a weight average molecular weight can be measured by methods, such as a gel permeation chromatography (GPC). If the weight average molecular weight is less than about 70,000, the moldability at the time of processing into a film deteriorates and there is a tendency for obtaining a sufficient thickness degree. Moreover, when a weight average molecular weight exceeds about 600,000, it will become difficult to shape | mold at the time of processing into a film, and it exists in the tendency for a gel-like foreign material to arise easily in a film.

Examples of such acrylic resins include alkyl polymethacrylates, copolymers of alkyl methacrylates and alkyl acrylates. The alkyl methacrylate unit content in the copolymer of alkyl methacrylate and alkyl acrylate is about 50 to 99% by weight, and the alkyl acrylate unit content is preferably about 50 to 1% by weight.

Examples of the alkyl methacrylate include methyl methacrylate. As the alkyl group in the alkyl acrylate, for example, an alkyl group having 2 to 10 carbon atoms is preferable, and specific examples of the alkyl acrylate include ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate and hexyl acrylate. And octyl acrylate.

Such acrylic resin is manufactured by a well-known bulk polymerization method, suspension polymerization method, etc. The glass transition temperature is adjusted according to the amount or type of copolymerization monomer used. The glass transition temperature generally increases as the amount of copolymerized monomer decreases, and decreases as the molecular weight of the copolymerized monomer increases. The weight average molecular weight is adjusted according to the kind and quantity of a polymerization initiator, the kind and quantity of a chain transfer agent, and polymerization temperature.

Although the acrylic resin used by this invention may be used as it is, without mixing the polymer obtained by superposition | polymerization with another polymer, the mixture of resin from which glass transition temperature or a weight average molecular weight differs may be sufficient. Even if the glass transition temperature or the weight average molecular weight is an acrylic resin different from about 60 to 110 ° C. or about 7 to 600,000, it can be used if their mixture satisfies the glass transition temperature of about 60 to 110 ° C. or the weight average molecular weight of about 7 to 600,000. have.

Among them, a mixture containing at least one resin component having a weight average molecular weight of about 70,000 to 200,000 is preferable in view of the surface hardness of the film. Moreover, the unevenness | corrugation at the time of thermoforming a film is a mixture containing the acrylic resin component of about 70,000-200,000, and the acrylic resin component of about 150,000-700,000 weight average molecular weight, respectively. It is preferable because the surface hardness can be obtained while sufficient surface hardness can be obtained. When such a mixture is observed on a chart of the molecular weight distribution measured by GPC, the peak has a shape with a gentle slope or a shoulder with respect to the molecular weight. The glass transition temperature of the resin component having a weight average molecular weight of about 70,000 to 200,000 is preferably about 90 to 110 ° C, and the glass transition temperature of the resin component having a weight average molecular weight of about 150,000 to 700,000 is preferably about 40-80 degreeC.

The multilayered acrylic polymer including the rubber elastomer layer is an acrylic polymer having a multilayer structure of two or more layers, preferably three layers. Such a multilayer structured acrylic polymer is, for example, (1) an inner layer and an outer layer, and the inner layer is a rubber elastomer made of a copolymer of a polyfunctional monomer such as alkyl acrylate having 4 to 8 carbon atoms of alkyl group and allyl methacrylate, and the outer layer. Is a two-layer structured acrylic polymer which is a hard polymer having a methyl methacrylate unit as a main component, and (2) an innermost layer, an intermediate layer and an outermost layer, and the innermost layer is a hard polymer having a methyl methacrylate unit as a main component. Is a rubber elastomer composed of a copolymer of a polyfunctional monomer such as alkyl acrylate ester having 4 to 8 carbon atoms of alkyl group and allyl methacrylate, and the outermost layer is a three-layer acrylic polymer which is a hard polymer containing methyl methacrylate unit as a main component. Etc. can be mentioned. Such a multilayered acrylic polymer can be produced, for example, according to the method described in Japanese Patent Publication No. 55-27576 (US Pat. No. 3,793,402).

The multilayered acrylic polymer including such a rubber elastomer layer has a particle diameter in the range of about 100 to 500 nm, preferably about 100 to 400 nm, more preferably about 250 to 350 nm. When the particle diameter is less than about 100 nm, the surface hardness of the film tends to be lowered, and when it exceeds about 500 nm, the transparency tends to be lowered.

The acrylic resin composition of the present invention needs to contain about 95 to 50 parts by weight of the acrylic resin and about 5 to 50 parts by weight of the multilayered acrylic polymer including the rubber elastomer layer. Here, the total amount of the multilayer structure acrylic polymer containing an acrylic resin and a rubber elastic layer is 100 weight part. If the multilayered acrylic polymer including the rubber elastomer layer is less than about 5 parts by weight, the film tends to be difficult to film, and if it exceeds 50 parts by weight, the surface hardness of the film tends to be lowered. The preferred composition ratio is about 10 to 30 parts by weight of the multilayered acrylic polymer including about 90 to 70 parts by weight of the acrylic resin and the rubber elastic layer.

The film of this invention may contain another polymer component, an additive, etc. in the range which does not impair the characteristic of the film of this invention. As another polymer component, fluorine resin, such as polyvinylidene fluoride, MS (methyl methacrylate-styrene) resin, etc. are mentioned, for example. Examples of the additive include weathering agents such as ultraviolet absorbers, antioxidants and light stabilizers, colorants such as dyes and pigments, flame retardants, and inorganic fillers.

As the ultraviolet absorber, for example, a benzotriazole ultraviolet absorber, a 2-hydroxybenzophenone ultraviolet absorber, a salicylic acid phenyl ester ultraviolet absorber, a benzophenone ultraviolet absorber and mixtures thereof are used.

Specific examples of the benzotriazole ultraviolet absorber include 2,2-methylenebis [4- (1,1,3,3-tetramethylenebutyl] -6- (2H-benzotriazol-2-yl) phenol], 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3, 5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3, 5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- (2 ' -Hydroxy-5'-t-octylphenyl) benzotriazole and the like, as 2-hydroxybenzophenone-based ultraviolet absorber, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxy Benzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxy-4'-chlorbenzophenone, 2,2-dihydroxy-4-methoxybenzophenone, 2,2-di Hydroxy-4,4'- dimethoxy benzophenone etc. are salicylic acid phenyl ester system ultraviolet rays Examples of the absorbent include para-salicylic acid para-t-butylphenyl, parasalicylic acid para-octylphenyl, etc., and these ultraviolet absorbers may be used alone or in combination of two or more thereof. The high molecular weight benzotriazole type ultraviolet absorber is preferable at the point which can prevent deterioration of the pattern printed on it, Specifically, for example, 2, 2-methylene bis [6- (2H benzotriazol-2-yl) -4 -(1,1,3,3-tetramethylbutyl) phenol] etc. are mentioned.

When using such a ultraviolet absorber, the usage-amount is about 0.1 weight part or more, preferably about 0.3-2 weight part per 100 weight part of acrylic resin composition.

Examples of the antioxidants include hindered phenol antioxidants, phosphorus antioxidants, sulfur antioxidants, and the like, and specifically hindered amine light stabilizers and the like.

The acrylic resin composition of the present invention can be produced by kneading a multilayered acrylic polymer including, for example, an acrylic resin and a rubber elastomer layer. When it contains another polymer component, an additive, etc., these may be contained in this acrylic resin, may be contained in the multilayer structure acrylic polymer containing a rubber elastic body layer, and may be contained in a multilayer structure acrylic system containing an acrylic resin and a rubber elastic body layer. It may be added when kneading the polymer. The conditions of kneading | mixing are not specifically limited, It can carry out by well-known kneading conditions.

After the acrylic resin composition of the present invention is extruded into a film shape to form a film, for example, a method of forming the film by contacting both surfaces or one surface thereof with a roll surface, and after extrusion molding with a film form, the both surfaces or one surface of the acrylic resin composition are formed on the belt. The film may be formed into a film by a method such as a belt cooling extrusion method which is brought into contact with each other, an inflation extrusion molding method, an extrusion casting by a chill roll, a solvent casting method, or the like.

Especially, it is preferable to shape | mold both surfaces of the film-form extruded in the film form in the state which contacted the roll surface or the belt surface from a viewpoint of the film thickness degree or surface smoothness. Moreover, although contacting a roll surface or a belt surface may be made to contact one surface after making it contact one surface, it is preferable to contact both surfaces simultaneously.

The temperature of the film when the both surfaces of the film is first contacted with the roll surface or the belt surface is at a temperature above the glass transition temperature of the acrylic resin composition, preferably at a temperature of about 20 ° C. or more higher than the glass transition temperature, and the roll or The linear pressure at the time of contact with the belt is about 50 to 150 kg / cm, preferably about 70 to 120 kg / cm.

As a material of a roll surface or a belt surface, a metal is preferable at the point which is excellent in cooling efficiency and the point which is easy to obtain the film excellent in smoothness, and can mention stainless steel, steel, etc. specifically ,. When steel is used, the surface may be treated with chromium plating or the like.

Although the surface temperature of a roll or a belt is not specifically limited, It is preferable to maintain at a constant temperature from the point which is easy to shape | mold into a film.

It is preferable to adjust the film thickness and surface state in multiple steps using the number of the metal rolls used 3-4 pieces.

Although the film obtained by such a method has sufficient thickness grade and surface smoothness, in order to further improve thickness grade and surface smoothness, you may cool after heating both sides or one side in the state which contacted the roll surface or the belt surface.

In addition, even if the acrylic resin film of the present invention contains foreign matters having a particle diameter of 100 μm or less, such foreign matters are removed when molded into a film because they have an effect on appearance or printability compared to conventional acrylic resin films. It is preferable to mold after the molding. If foreign matter is present on the surface, printing leakage or the like is more likely to occur when a pattern or the like is applied to one or both surfaces of the film by printing or the like.

In order to remove foreign substances, it is preferable to arrange | position a metal screen mesh, a ceramic screen mesh, etc. in the channel | path of the molten resin of an acrylic resin composition, for example. In particular, it is preferable to use a rotary screen changer in view of low loading and low stopping frequency of the production process for eliminating loading. Examples of such rotary screen changers include "No. KSF-45 x 2" manufactured by Gnoise Corporation (Germany). By installing such a rotary screen changer in the passage of the molten resin, extruding the resin, and molding into a film, an acrylic resin film substantially free of foreign matter having a particle diameter of 100 µm or less can be obtained.

The thickness of the acrylic resin film of the present invention is about 0.05 to 1 mm, preferably about 0.1 to 0.6 mm. Here, the "film" includes not only a so-called film shape but also a sheet-like thing.

The acrylic resin film of the present invention may be patterned or colored on one or both surfaces thereof. In addition, a pattern or the like may be printed on the colored film. When printing a pattern, the base underprint layer can be omitted depending on the colored film.

As a coloring method of a film, the method of using colored resin as a raw material, or the method of dyeing a transparent film in a later process is possible. As an example of a coloring method, the method of immersing and dyeing in alcohol containing 10-30 g / L of alcohols, such as benzyl alcohol, in the liquid which disperse | distributed the disperse dye was mentioned.

Moreover, you may form an adhesive layer, an adhesive bond layer, etc. in one side of the acrylic resin film of this invention. Such an adhesive layer or an adhesive layer can be easily formed by coating a conventional method, for example, an adhesive or an adhesive (hereinafter referred to simply as an adhesive).

Since the acrylic resin film of the present invention has a sufficient thickness and excellent surface smoothness and sufficient surface hardness, it can be used, for example, as an injection molding co-adhesive film, agricultural film, display film, masking film and the like.

Injection molding co-adhesion using the acrylic resin film of the present invention is made of, for example, male and female, and opens the male and female molds of a male and female mold having a cavity space to insert the acrylic resin film of the present invention between both molds. The mold is filled in the state in which the film is sandwiched between the two molds, and then, the thermoplastic resin in the molten state is injected into the cavity space and supplied, followed by cooling. As a result, a laminated molded product obtained by adhering the film of the present invention to the surface of a molded product made of a thermoplastic resin can be obtained.

The acrylic resin film of the present invention supplied between molds may be molded into a desired shape by vacuum molding or the like in advance. In this case, the thickness of the film is preferably in the range of about 0.1 to 0.5 mm from the standpoint of formation. When shaping to the desired shape, the mold preformed with the mold for molding may be supplied between the female molds used for injection molding, but the molds may be molded using either mold and not removed from the mold. Injection molding simultaneous bonding may be performed.

In addition, although the film may be supplied between molds one by one, it can also supply, winding a continuous film off a roll. In this case, it is preferable that the thickness of a film is about 0.6 mm or less from the point which is easy to wind up in roll shape, and it is preferable that it is about 0.2 mm or less from a viewpoint of winding weight (roll weight). In the case of thickness of about 0.2 mm or more, it can supply between molds one by one in screen state.

In the case of using a pattern on which one surface of the acrylic resin film of the present invention is transparent by printing or the like, when the molten thermoplastic resin is supplied to the surface on which the pattern of the film is applied, the laminated molded product obtained has a pattern as a clear layer. It is desirable to have a sense of depth in the pattern to be placed above. In this case, the thickness of the film is preferably about 0.1 mm or more because a sufficient sense of depth can be obtained.

Thermoplastic resins supplied by injection into the cavity space include, for example, acrylonitrile-butadiene-styrene resins (ABS resins), polycarbonate resins, polystyrene resins, polyolefin resins, and the like. In view of stability, ABS resins, polycarbonate resins, or impact-resistant polypropylene resins are preferable. Moreover, when such a thermoplastic resin contains acrylic resin, since the adhesive strength of the thermoplastic resin in the laminated molding obtained and the film of this invention improves, it is preferable. In the case where the acrylic resin is contained in the thermoplastic resin, the content thereof is preferably about 10% by weight or less.

The temperature, injection pressure, and the like of the thermoplastic resin in injection molding are appropriately selected depending on the type of resin to be injected, the target laminated molded product, the position of the injection gate in the mold, and the like.

In addition, when olefin resin etc. are used as a thermoplastic resin, in order to provide adhesiveness with the acrylic resin film of this invention, you may perform a base process to the surface which adhere | attaches the thermoplastic resin of a film.

As the base treatment, for example, a method of coating the chlorinated polypropylene resin in advance can be used.

The acrylic resin film of the present invention has excellent transparency and low heat transmittance (infrared ray) with a light transmittance (far-infrared ray) having a wavelength of 3000 nm or more, as well as general acrylic resin film. Can also be used as a film. Since conventional acrylic resin films have had a low surface hardness, when used for a long time, transparency tends to be lowered due to scratches caused by dust, sand, etc., and there is a problem when used as an agricultural film. On the other hand, since the acrylic resin film of this invention has a sufficiently hard surface, since transparency falls little by friction of sand, dust, etc., it can be used practically as an agricultural film.

When using the acrylic resin film of this invention for agricultural films, in order to provide blur prevention property, you may contain 1 or more types, such as a hydrophilic polymer and surfactant, and may apply to a film surface. The method of making a hydrophilic polymer and surfactant into a film, and the method of apply | coating to a film surface can be performed by a well-known method.

Since the acrylic resin film of the present invention is excellent in surface smoothness, printing, gravure printing, screen printing, etc., may be performed on one surface thereof by an ink jet printer. The acrylic resin film of the present invention subjected to such printing can be used as an exterior, advertising or promotional display film, namely a marking film, by forming an adhesive layer or the like on the opposite side to the printed side. Such display films are printed and used by various characters, patterns, photographs, etc. by printing by an ink jet printer using computer graphics technology.

As a display film, a soft vinyl chloride resin film, a polyurethane resin film, a polyethylene terephthalate film, etc. have been used conventionally, but the display film using the acrylic resin film of this invention originates in weather resistance and transparency compared with these conventional display films. The appearance of the pattern is excellent.

When using the acrylic resin film of this invention as a display film, it is preferable that total light transmittance (Tt) is 91% or more and haze is 2% or less.

Moreover, it is preferable that the thickness of the adhesive layer formed in one side is about 15-60 micrometers, for example. Examples of the pressure-sensitive adhesives include acrylic pressure-sensitive adhesives and polyurethane pressure-sensitive adhesives obtained by radical polymerization of a vinyl monomer composition containing an acrylic vinyl monomer and vinyl acetate in a solution. Such an adhesive layer can be formed by laminating | stacking with an acrylic resin film, after apply | coating an adhesive to a peeling material by coating methods, such as a reverse roll coating method, and drying it for heating. Although it does not specifically limit as a peeling material here, For example, a silicone coating type release paper etc. are used.

The display film obtained by such a method can be cut into the shape of desired size, a figure, a character, etc. as needed, for example, can peel a mold release material, and can laminate | stack it on the target coating material. The coating base material may be a plastic molded body, glass, metal, wall material, wood, or the like. Examples of the plastic molded article include acrylic resins, acrylonitrile-butadiene-styrene resins, polycarbonate resins, vinyl chloride resins, polystyrene resins, and polyolefin resins.

Applications of such display films include outdoor signage (rooftops, retail signs, pole signs, field signs, canopy signs, etc.), guide signs (introduction signs, display signs, guide signs, station yard signs, etc.), commercial Marking for vehicles (pleat marking), marking for shutters and exterior walls, marking for factories and boards at construction sites, marking for vending machines, marking for construction machinery, marking for railway vehicles, marking for ships, tents Markings on seats, passenger cars as inline members, trucks, motorcycles, pharmacopoeia, and the like, wall coverings as interior decorations, planks underneath, imitation, and the like.

Since the acrylic resin film of this invention is excellent also in transparency, it can be used also as a masking film for the purpose of protecting a base material, for example.

As a masking film, a pressure-sensitive adhesive layer formed on a polystyrene resin film has been conventionally used. However, since the polyethylene-based resin has crystallinity and is generally translucent, the masking film is peeled off after visual inspection of the synthetic resin plate. It needs to be done. In addition, there is a problem that optical deformation (optical anisotropy) is likely to occur, and therefore, when used as a masking film of an optical film, it is necessary to perform inspection such as optical deformation of the optical film by peeling off the masking film.

On the other hand, since the masking film using the acrylic resin film of this invention is excellent in transparency, visual inspection, such as an acrylic resin plate and a polycarbonate resin plate, can be performed, without peeling off a masking film. In addition, when used as a masking film of an optical film, such as a polarizing film, a retardation film, there is no optical deformation can be carried out without peeling off the masking film, such as optical deformation of the optical film or the labeling.

The acrylic resin film of this invention can also be set as the laminated | multilayer film in which the other film layer was laminated | stacked on the one side. As another film layer, the film of a normal acrylic resin, a vinyl chloride resin, an acrylonitrile butadiene-styrene copolymer, a polycarbonate resin, and an olefin resin is mentioned, for example.

Although the thickness of another film layer is not specifically limited, It is the range of about 0.05-5 mm, Preferably it is about 0.1-3 mm. The other film layer may be one layer or two or more layers.

Such a laminated film may be produced by, for example, a multilayer extrusion method of simultaneously extruding and laminating the acrylic resin film layer of the present invention and another film layer, or may be produced by bonding the acrylic resin film of the present invention and the other film, respectively. Further, the other film layer may be extruded in a film shape, and the acrylic resin film of the present invention may be adhered to this film in a heated state immediately after extrusion molding, and immediately after the adhesion, the film of the acrylic resin film of the present invention and other films The laminated film can be obtained by contacting the layer with the roll surface or the belt surface.

When such a laminated film uses film layers other than an acrylic resin film layer as another film layer, it is preferable to use it so that the outer side may become the acrylic resin film of this invention from a surface clear and transparency can be obtained.

In addition, when a laminated film is an acrylic resin film layer and the acrylic resin film layer of this invention, the outer side is a normal acrylic resin film layer (for example, the acrylic resin film layer which does not contain a rubber elastic body), and the inside is the inside of this invention. It can also be used so that it may become an acrylic resin film layer. In this case, it can also be set as the laminated film excellent in the surface hardness, chemical-resistance, and weather resistance of a laminated film.

Moreover, although a normal acrylic resin film alone is difficult to wind up in roll shape, since such laminated | multilayer film can be wound up in roll shape, it is also advantageous in this point.

Even in such a laminated film, a non-colored acrylic resin film and a colored acrylic resin film, or a non-colored acrylic resin film and a laminated olefin resin (especially an impact resistant polypropylene resin) film may be used as a non-colored acrylic resin film. The colored film layer is seen as a deep color through the effect that the sense of quality is increased. Further, by containing 1 to 10% by weight of metal powder (particularly flat aluminium powder, etc.), mica, and the like in the colored or non-colored film layer, it becomes possible to achieve an effect called a metallic or pearly.

Such laminated films are particularly useful as paint substitutes for automotive exteriors such as bumpers, garnishes, side malls or home appliances such as refrigerators, air conditioners, washing machines, etc., in that acrylic resin films have excellent weather resistance and surface hardness. By using this coating substitute film, environmental pollution by the organic solvent contained in the paint used for general coating can also be prevented. Such a laminated film is usually used so that a non-colored acrylic resin film is outward, and other resins by injection molding, metals by adhesion, or the like can be used as the base.

When adhering an acrylic resin film and a colored olefin resin film, chlorinated polypropylene resin, ethylene-methyl methacrylate copolymer resin, maleic anhydride modified polypropylene resin, etc. are contained in the olefin resin film, or these resins It is effective to apply the coating on the surface.

Moreover, acrylic resin film and colored olefin resin can also be laminated | stacked by the lamination method using a urethane type adhesive etc.

In the case of laminated | multilayer film, printing of a pattern may be in the surface of an acryl-type film, and may be in the surface of another film. For example, in the case where the other film layer is a vinyl chloride resin film, a pattern or the like can be easily printed on one side thereof, and by laminating the acrylic resin film of the present invention thereon, the film is made into a laminated film having transparency and excellent designability. Can be. Lamination can be performed, for example by heating and pressurizing the acrylic resin film and the vinyl chloride resin film of this invention, and a heating temperature is about 80-200 degreeC.

The laminated film can be used, for example, for agricultural materials such as greenhouses, construction materials such as arcades, soundproof panels, and outdoor decorative materials such as sunroofs.

The laminated | multilayer film can be used for the injection molding co-adhesive film, the agricultural film, and a display film like a single layer acrylic resin film.

When using for the injection molding co-adhesion method, it can carry out by the same method as the acrylic resin film of this invention mentioned above.

Moreover, when using it for agricultural films, a preferable other film is a vinyl chloride resin film, a polyolefin resin film, a polyvinyl alcohol resin film, a polyethylene terephthalate film, a polycarbonate film, etc. are mentioned, for example.

Furthermore, when using as a display film, it is used so that the acrylic resin film of this invention may become outermost layer, and an adhesive layer is formed in the surface of the other film layer side. The other film layer may be colored, and a pattern may be formed by printing or the like between the acrylic resin film of the present invention and the other film layer. When the acrylic resin film of this invention becomes an outermost layer, a sense of depth appears in these and designability improves.

It is preferable that the total light transmittance (Tt) of the acrylic resin film in such a display film is 91% or more, and haze is 2% or less. In addition, the adhesive which comprises the adhesive layer formed in one surface, and the thickness are the same adhesive and thickness as when using a single layer acrylic resin film as a display film, and can be formed as an adhesive layer by the same method as mentioned above. . In addition, a use method and a use are also the same as the case where the acrylic resin film of this invention is used for a display film.

The acrylic resin film of the present invention and the multilayer film thereof are suitable for various applications such as injection molding co-adhesive film, agricultural film, display film, masking film and paint substitute film. Especially when the film which colored on this film and printed the pattern etc. is laminated | stacked compared with the conventional acrylic film, it is excellent in the printability of the depth, high quality, etc., or pattern.

Best Mode for Carrying Out the Invention

Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these Examples.

The evaluation method is as follows.

(1) Thickness

Using a dial gauge about 1/1000 mm, the thickness of the film was continuously measured for each 1 m in the width direction and the take-out direction, and the average thickness (d _o ), the maximum thickness (d _max ), and the minimum thickness (d _min ) were measured. ) And calculate the thickness of the larger of the difference between the average thickness (d _o ) and the maximum thickness (d _max ) or the difference between the average thickness (d _o ) and the minimum thickness (d _min ) as Δd.

Thickness Accuracy (%) = (Δd / d _o ) × 100 (1)

Calculate by

(2) Unevenness generation test during molding

The surface state of the obtained laminated molded product is visually observed and determined by the following criteria.

: Almost no surface irregularities.

(Triangle | delta): There are some unevenness | corrugations on the surface.

Ｘ: There are minute irregularities on the surface.

(3) gauze wearability

Wear tester for measuring the color fastness [Toyosei Seisakusho Co., Ltd. type D] is equipped with a gauze and subjected to 500 round trip abrasion test with a load of 200 g. do.

: No wear.

(Triangle | delta): There is a little wear.

T: There is clear wear.

(4) surface hardness

Pencil hardness is measured according to JIS K 5400.

(5) optical performance

The total light transmittance (Tt) and haze are measured in accordance with JIS K 6718.

(6) glass transition temperature

The endothermic onset temperature observed when heating up at a temperature increase rate of 10 ° C./min under N ₂ airflow using a differential scanning calorimetry (DSC) is measured by a tangential method.

(7) weight average molecular weight

It is measured by gel permeation chromatography (GPC).

(8) Number of missing prints

Gravure is printed on one side of the film, and the number of printing missing points is visually inspected on the front side of the film having a width of 1 m and a length of 10 m, and the number is converted into per 1 m 2.

In addition, the meaning of each symbol in an Example is as follows.

① Acrylic resin Ⅰ:

A resin produced by a bulk polymerization method comprising 99% by weight of methyl methacrylate units and 1% by weight of methyl acrylate units, having a glass transition temperature of 106 ° C. and a weight average molecular weight of 140,000.

② Acrylic resin Ⅱ:

A resin produced by a bulk polymerization method comprising 90% by weight of methyl methacrylate units and 10% by weight of methyl acrylate units, having a glass transition temperature of 95 ° C. and a weight average molecular weight of 120,000.

③ Acrylic resin Ⅲ:

A resin produced by the suspension polymerization method, comprising 80% by weight of methyl methacrylate units and 20% by weight of butyl acrylate units, having a glass transition temperature of 62 ° C. and a weight average molecular weight of 300,000.

④ Acrylic resin Ⅳ:

A resin produced by the suspension polymerization method, comprising 80% by weight of methyl methacrylate units and 20% by weight of butyl acrylate units, having a glass transition temperature of 62 ° C. and a weight average molecular weight of 500,000.

⑤ Acrylic resin Ⅴ:

A resin produced by the suspension polymerization method, comprising 70% by weight of methyl methacrylate units and 30% by weight of methyl acrylate units, having a glass transition temperature of 47 ° C and a weight average molecular weight of 300,000.

⑥ Acrylic polymer A:

The innermost layer was manufactured by the following method with reference to Example 3 of JP-A-55-27576, and the innermost layer was a methyl rubber methacrylate crosslinker, and the middle layer was a soft rubber elastomer and the outermost layer. A spherical three-layered acrylic polymer composed of methyl methacrylate polymer. The average particle diameter of this polymer particle is about 300 nm.

100 parts by weight (parts by weight) of distilled water, potassium carbonate as a pH adjuster, dioctyl sulfosuccinate as an emulsifier and potassium persulfate as a polymerization initiator were added and stirred under a nitrogen atmosphere, followed by 38 parts of methyl methacrylate and methacryl. Add 0.08 parts of acid allyl. These mixtures are reacted at 70 ° C. for 30 minutes to obtain an innermost polymer. Subsequently, 38 parts of butyl acrylate, 9 parts of styrene, and 1 weight part of allyl methacrylates, and a mixture of potassium persulfate and dioctyl sulfosuccinate were continuously added over 90 minutes, and the mixture was kept at 85 ° C. for 90 minutes to form an intermediate layer. The crosslinked elastic layer of is polymerized. Finally, a mixture of 14 parts of methyl methacrylate, 0.6 parts of ethyl acrylate, and potassium persulfate was continuously added over 60 minutes, and further maintained at 85 ° C. for 60 minutes to polymerize the outermost layer. Obtain a polymer. The final average particle diameter of this polymer particle measured by the electron microscope is 300 nm. The polymer latex is condensed according to the conventional method, and then dehydrated and dried to obtain a dry powder.

⑦ Acrylic polymer B:

A spherical two-layer structured acrylic polymer produced in accordance with the manufacturing method of the acrylic polymer A without forming an innermost layer, wherein the inner layer is a soft rubber elastic body mainly containing butyl acrylate and the outer layer is a methyl methacrylate polymer. The average particle diameter of this polymer particle is about 300 nm.

⑧ UV absorber LA31:

Asahi Tenka Kogyo Co., Ltd. LA-31 (high molecular weight benzotriazole)

⑨ UV absorber 250:

Sumitomo Kagaku Kogyo Co., Ltd. 250

⑩ Alumina Powder:

Toyo Alumi Co., Ltd.

⑪ Titanium oxide powder:

Kantokagaku Co., Ltd., titanium oxide powder

⑫ Disperse Dyes:

Sumitomo Kagaku Kogyo Co., Ltd. E-FBL

TECHNICAL FIELD The present invention relates to an acrylic resin film and a laminated film thereof, and more particularly, to their use.

Reference Example

Each raw material is mixed with a tumbler mixer at the composition ratio shown in Table 1, and melt-kneading while maintaining the resin temperature of 255 degreeC using the twin-screw extruder of co-rotation, and pellets of acrylic resin compositions a-i are obtained.

Examples 1-8

Pellets of each acrylic resin composition shown in Table 2 were subjected to a T-type film die [lip clearance 0.5 mm, width 600 mm, set temperature 250 ° C.] using a single screw extruder [Toshiba Kikai Co., Ltd., barrel diameter 65 mmø]. It is extruded to obtain a film, immediately molded on both surfaces of the cold polishing roll surface at the same time and completely connected to obtain an acrylic resin film [thickness 0.13 mm]. Table 2 shows the results of the evaluation of this film.

A pattern of wood grain is printed on one side of the film, placed in a cavity of an injection molding die (mold temperature of 50 ° C.) consisting of a pair of male and female molds and heated with a far infrared heater, followed by vacuum molding. Implement and shave. Subsequently, the heat-melted ABS resin [resin temperature 230 ° C.] is injected at an injection pressure of 1150 kg / cm 2, and then cooled to obtain a laminated molded product having an acrylic resin film adhered to the surface of the ABS resin molded body. Table 2 shows the evaluation results of the laminate.

Examples 9 and 10

In Examples 1 and 4, instead of contacting both surfaces of the film-like article on the surface of the cooling polishing roll, the same operation was performed except that only one side of the film-shaped article was brought into contact with the cooling polishing roll surface to obtain an acrylic resin film [thickness 0.13 mm], Subsequently, a laminate is obtained. Table 2 shows the evaluation results of the acrylic resin film and the laminated molded product.

Example 11

Both surfaces are heated and cooled in the state which contacted the acrylic resin film obtained in Example 10 with the continuous stainless steel belt, and an acrylic resin film is obtained. Table 2 shows the results of the evaluation of the acrylic resin film.

A laminated molded product was obtained in the same manner as in Example 1 except that the acrylic resin film obtained above was used instead of the acrylic resin film obtained in Example 1. Table 2 shows the evaluation results of the laminate.

Example 12

Example on the surface of a polycarbonate resin sheet being extruded through a T-shaped film die [lip clearance 4 mm, width 600 mm, set temperature 280 ° C.] using a single-screw extruder [manufactured by Toshiba Kikai Co., Ltd., barrel diameter 65 mmø]. The acrylic resin film obtained in 1 is laminated | stacked simultaneously with extrusion, and both surfaces contact a polishing roll completely, and a laminated film (thickness 3m) is obtained. Table 2 shows the evaluation results of this laminated film.

Example 13

A laminated film (thickness 3 mm) was obtained in the same manner as in Example 12 except that the acrylic resin film obtained in Example 4 was used instead of the acrylic resin film obtained in Example 1. The evaluation results of the laminated film are shown in Table 2 below. Indicates.

Example 14

The laminated resin is obtained by laminating the acrylic resin film obtained in Example 1 on the printed pattern side of the flexible vinyl chloride film having a thickness of 0.1 mm in which a carbon pattern is printed on the surface.

The laminated film was molded by thermoforming, and then inserted into a mold for injection molding (mold temperature of 50 ° C.), followed by injection molding of polycarbonate resin [injection pressure 1250 kg / cm 2, resin temperature of 280 ° C.] for simultaneous injection molding. To obtain a laminated molded product obtained by laminating a laminated film on a polycarbonate resin layer (thickness 3 mm).

Example 15

An inorganic red pigment is kneaded into the composition (d) to obtain pellets of the composition (d '), and the pellet is fed to a single screw extruder (manufactured by Toshiba Kikai Co., Ltd., barrel diameter 65 mm). In addition, the pellet of the composition (i) is supplied to a single screw extruder (manufactured by Hitachi Josen Co., Ltd., barrel diameter 45 mm). The composition (d ') and the composition (i) were extruded from each single screw extruder through a two-layer multi-manifold film die [lip clearance 0.5 mm, width 600 mm, set temperature 250 ° C.] connected to both single screw extruders and cooled. Both surfaces of the polishing roll (made of stainless steel) are completely brought into contact with each other to be molded to obtain a laminated film having a thickness of 0.3 mm (0.2 mm of red layer and 0.1 mm of transparent layer). Table 2 shows the evaluation results of this laminated film.

The laminated film was placed in an injection molding mold (temperature 50 ° C.) so that the transparent layer was in contact with the mold surface, heated with a far infrared heater, and then vacuum molded, and then acrylonitrile-butadiene-styrene resin (ABS) was formed on the surface thereof. Resin) is injected (injection pressure 1150 kg / cm 2, resin temperature 230 ° C.) to perform injection molding co-adhesion to obtain a laminated molded product in which a laminated film is laminated on an ABS resin layer (thickness 3 mm). Table 2 shows the evaluation results of the laminate.

Example 16

The composition obtained by mixing the aluminum paste so as to be 2 parts by weight in terms of alumina in 100 parts by weight of the composition (b) was granulated using a twin screw extruder (manufactured by EIGEITECH Co., Ltd., PCM-45) and colored in silver metallic color. Get pellets.

The colored pellets are supplied to a single screw extruder [manufactured by Toshiba Kikai Co., Ltd., barrel diameter 65 mmø], and the pellets of the composition (i) are fed to a single screw extruder [manufactured by Hitachi Josen Co., Ltd., barrel diameter 45 mmø]. Through a feed block-type multi-layer die connected to two extruders (Hitachijosen Co., Ltd., lip face length 600 mm), a laminated film consisting of a transparent acrylic resin film and a lower layer of silver metallic acrylic resin film is cooled and polished (stainless steel). The mold is formed by completely contacting both surfaces with The film thickness is 0.5 mm.

This film is a silver metallic laminated film with a deep surface gloss.

The chlorinated polypropylene resin ("No.822" manufactured by Nippon Seishi Co., Ltd.) was coated on the lower layer side of the laminated film, and then placed in an injection molding mold (temperature 50 ° C) so that the surface layer contacted the mold surface. After heating with a heater, vacuum molding (area development rate 1.3 times) is performed.

Subsequently, polypropylene resin (Sumitomo Kagaku Kogyo Co., Ltd. make, "Sumitomo noble" BYA81 '') was injected (injection pressure 1150 kg / cm 2, resin temperature 250 ° C) to perform simultaneous injection molding, and a laminate of silver metallic laminated films integrally laminated on a polypropylene resin layer (thickness 3 mm). Obtain a molded body. The surface of the laminated molded product has a deep surface gloss, and the polypropylene resin layer and the laminated film are firmly bonded.

Example 17

A pellet colored in white was obtained in the same manner as in Example 16, except that 5 parts by weight of titanium oxide powder was used in terms of titanium oxide instead of aluminium pest.

Instead of the silver metallic colored pellets, the colored pellets were used to mold the laminated film in the same manner as in Example 16. The film thickness is 0.5 mm.

This film is a white laminated film with a deep surface gloss.

Example 18

10 g / l of the red dispersion is dispersed in distilled water containing 18 g / l of benzyl alcohol, and the acrylic resin film (0.13 mm thick) obtained in Example 1 is immersed and dyed in a dyeing solution heated to 80 ° C.

The result of having examined the color tone of this dyed film by the color difference display method of JISZ-8730 is L * = 86.0, a * = 22.8, b * =-5.4, and is uniform.

When gravure printing a grain-shaped pattern on one side of the film, the base base print layer on the front surface is omitted, and the printing is completed only on the pattern.

Comparative Example 1

Commercially available soft acrylic film [Mitsubishi Leyong Acreprene HBS-001, thickness of 100 μm], the same wood grain pattern as in Examples 1 to 8 was printed, and the printed film was heated with a far-infrared heater in an injection molding mold (temperature 50 ° C.), followed by vacuum molding. On the back side thereof, an ABS resin was injected to a thickness of 3 mm (injection pressure 1150 kg / cm 2, resin temperature 230 ° C.) to obtain a laminate with a printed film.

Table 2 shows the evaluation results of the obtained film and the laminated molded product.

In addition, the present acrylic film HBS-001 contained a large number of single-layer rubber elastomers having a particle diameter of less than 100 nm, but it was confirmed by observing with a transmission electron microscope that the acrylic polymer of the multilayer structure was not contained.

Composition Name Acrylic resin Acrylic polymer (parts by weight) UV absorber (parts by weight) (Parts by weight) Tg (℃) Mw × 10 ⁴ I Ⅱ Ⅲ Ⅳ Ⅴ A B LA31 250 a 80 106 14 20 0.5 b 75 95 12 25 One c 80 62 30 20 0.5 d 30 50 78 23 20 0.5 e 25 50 83 37 25 One f 30 50 65 23 20 0.5 g 80 106 14 20 0.5 h 30 50 78 23 20 0.5 i 100 106 14 One Tg: glass transition temperature Mw: weight average molecular weight

Example Type of composition Properties of the film Performance of Laminated Parts Thickness Optical performance Number of prints missing Surface hardness Gauze wear resistance Molding irregularities Tt (%) Haze (%) One a 5 93 0.8 0.1 H △ 2 b 6 93 0.9 0.2 H △ 3 c 7 92 1.1 0.3 2B △ 4 d 6 93 0.9 0.2 HB 5 e 7 92 1.0 0.4 HB △ 6 f 8 92 1.2 0.3 B △ 7 g 6 93 0.9 0.3 B △ 8 h 6 92 1.1 0.4 B △ 9 a 8 92 2.5 8.2 HB △ △ 10 d 9 92 3.6 7.8 B △ 11 d 9 93 0.2 0.1 HB 12 a 5 93 0.8 - H 13 d 6 93 0.9 - HB 14 a 5 93 0.8 0.1 HB △ 15 i 5 - - - 2H Comparative Example 1 14 92 1.4 14.0 5B Ｘ

Claims (16)

Acrylic resin consisting of an acrylic resin composition containing 95 to 50 parts by weight of an acrylic resin having a glass transition temperature of 60 to 110 ° C. and a weight average molecular weight of 70,000 to 600,000, and 5 to 50 parts by weight of a multilayered acrylic polymer including a rubber elastic layer. film. The acrylic resin film according to claim 1, wherein the acrylic resin is at least one polymer selected from the group consisting of alkyl polymethacrylate and a copolymer of alkyl methacrylate and alkyl acrylate. 2. The rubber according to claim 1, wherein the multilayer structured acrylic polymer comprising a rubber elastic layer comprises (1) an inner layer and an outer layer, and the inner layer is made of a copolymer of alkyl acrylate having 4 to 8 carbon atoms of an alkyl group and a polyfunctional monomer. It is an elastic body, and an outer layer consists of a 2-layered acrylic polymer which is a hard polymer which has a methyl methacrylate unit as a main component, and (2) an innermost layer, an intermediate | middle layer, and an outermost layer, and an innermost layer has methyl methacrylate unit as a main component. It is a hard polymer, the middle layer is a rubber elastic body composed of a copolymer of alkyl acrylate having 4 to 8 carbon atoms of an alkyl group and a polyfunctional monomer, and the outermost layer is a three-layer structure acrylic polymer which is a hard polymer mainly composed of methyl methacrylate units. Acrylic resin film which is 1 or more types of polymers chosen from the group which consists of. The acrylic resin film according to claim 1, wherein the multilayered acrylic polymer has a particle diameter of 100 to 500 nm. The acrylic resin film of Claim 1 shape | molded in the state which contacted the roll surface or the belt surface both surfaces of the film-form object obtained by melt-extrusion molding an acrylic resin composition. The acrylic resin film according to claim 1, which is colored by a dyeing method. The laminated | multilayer film formed by laminating | stacking another resin film layer on one side of the acrylic resin film of Claim 1. The laminated film according to claim 7, wherein the other resin film is a vinyl chloride resin film. The laminated film according to claim 7, wherein the other resin film is a colored acrylic resin film or a colored olefin resin film. The laminated film according to claim 9, wherein the colored acrylic resin film or the colored olefin resin is obtained by adding metal powder or mica. The method of using the acrylic resin film of Claim 1 as a masking film. The method of using the film of Claim 1 or 7 as a film for injection molding co-adhesion. The method of using the film of Claim 1 or 7 as an agricultural film. The method of using the film of Claim 1 or 7 as a display film. The method of using the film of Claim 9 as a coating substitute film. The laminated molded object formed by inserting the film of Claim 1 or 7 into a female mold, and simultaneously bonding this film to the surface of the molded object obtained by injection molding a thermoplastic resin in a metal mold.